(3-Aminopropyl)triethoxysilane → HCID 178476782, compound

HRID 448833Notes

Reaction equation

HRID 448833 reaction equation
I[C:2]1[CH:7]=[CH:6][C:5]([C:8]([F:11])([F:10])[F:9])=[CH:4][CH:3]=1.[PH2:12]([O-:14])=[O:13].[NH3+][C:16]1C=CC=C[CH:17]=1.NCCC[Si](OCC)(OCC)OCC.C1(P(C2C=CC=CC=2)CCCP(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>C(#N)C.C(OCC)(=O)C.Cl.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[F:9][C:8]([F:11])([F:10])[C:5]1[CH:6]=[CH:7][C:2]([PH:12](=[O:14])[O:13][CH2:16][CH3:17])=[CH:3][CH:4]=1

Participants

9

Reactant 4

HCID 13521(3-Aminopropyl)triethoxysilaneHCID 67993Benzene, 1-iodo-4-(trifluoromethyl)-HCID 812191,3-Bis(diphenylphosphino)propaneHCID 178527020HCID 178527020, compound

Product 1

HCID 178476782HCID 178476782, compoundYield 28%

Reagents, catalysts & solvents 4

HCID 167845palladium(II) acetateCatalystHCID 313Hydrochloric AcidSolventHCID 6342AcetonitrileSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a degassed solution of 4-iodobenzotrifluoride (4.70 g, 17.2 mmol), anilinium hypophosphite (3.51 g, 22.1 mmol), and 3-aminopropyl triethoxysilane (4.88 g, 22.1 mmol) in anhydrous acetonitrile (110 mL) were added palladium acetate (82.5 mg, 0.367 mmol, 2 mol %) and 1,3-bis(diphenylphosphino)propane (167 mg, 0.404 mol, 2.2 mol %). The mixture was refluxed for 32 hrs. After cooling down to room temperature, the reaction mixture was diluted with ethyl acetate and hydrochloric acid (1M), and partitioned. The aqueous layer was further extracted with ethyl acetate. The combined extracts were washed sequentially with aqueous sodium hydrogen carbonate and brine, dried over magnesium sulfate, and concentration in vacuo. The resulting residue was purified by column chromatography using 25 to 100% ethyl acetate in petroleum ether. Further purification by distillation afforded compound AZ1 (1.14 g) in 28% yield. 1H NMR (CDCl3, 400 MHz): δ (ppm) 1.35-1.43 (m, 3H), 4.12-4.27 (m, 2H), 7.63 (d, J=570.8 Hz, 1H), 7.75-7.80 (m, 2H), 7.90-7.94 (m, 2H); 31P NMR (CDCl3, 161.8 MHz): δ (ppm) 22.6.

Workup

  1. temperatureThe mixture was refluxed for 32 hrs
  2. custompartitioned
  3. extractionThe aqueous layer was further extracted with ethyl acetate
  4. washThe combined extracts were washed sequentially with aqueous sodium hydrogen carbonate and brine
  5. dry with materialdried over magnesium sulfate, and concentration in vacuo
  6. customThe resulting residue was purified by column chromatography
  7. customFurther purification
  8. distillationby distillation
  9. customafforded compound AZ1 (1.14 g) in 28% yield

Sources & evidence

ORD record
ord-6997865f47c44884a4e11bdf64aa9629
Source dataset
uspto-grants-2013_07
Patent number
US08481748B2

Reaction notes

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